ES2217859T3 - ZWITTERIONIC TRANSITION METAL COMPOSITE, NEUTRAL. - Google Patents

Abstract

A boron-containing zwitterionic neutral transition metal compound which can advantageously be used for the polymerization of olefins is described. Here, the use of aluminoxanes, such as methylaluminoxane (MAO), as a cocatalyst can be dispensed with and a high catalyst activity and a good polymer morphology can nevertheless be achieved.

Description

Zwitterionic transition metal compound, neutral.

The present invention describes a compound of Zwitterionic transition metal, neutral, which can be used advantageously for the polymerization of olefins. In this case it can dispense with the use of aluminoxanes, such as methylaluminoxane (MAO) as a cocatalyst, and get, however, a high catalyst activity and good polymer morphology.

The role of cationic complexes in the polymerization of Ziegler-Natta with metallocenes is generally recognized (H. H. Brintzinger, D. Fischer, R. Mülhaupt, R. Rieger, R. Waymouth, Angew. Chem. 1995, 107, 1255-1283).

MAO, as an effective co-catalyst, It has the disadvantage of having to use it in high excess. The synthesis of cationic alkyl complexes opens the possibility of obtain MAO-free catalysts with comparable activity, the co-catalyst can be used in quantity Almost stoichiometric. The synthesis of alkyl complexes cationic opens the possibility of obtaining catalysts free of MAO with comparable activity, being able to use the co-catalyst in almost quantity stoichiometric

The synthesis of catalysts of polymerization of metallocene "cation-like" in J. Am. Chem. Soc. 1991, page 3623. A procedure is claimed for the  obtaining salts of the general formula LMX + XA - according to the principle described above in EP 520 732.

EP 558 158 describes catalyst systems zwitterionics that are synthesized from compounds of metallocenodialkyl and salts of the formula [R 3 NH] + [B (C 6 F 5) 4] -. The reaction of such salt, for example, with Cp 2 ZrMe 2 provides a zirconocenomethyl cation as an intermediate by Protolysis under methane removal. This reacts through activated C-H to give zwitterion Cp 2 Zr + - (m-C 6 H 4) - BPh 3 -. In this case, the Zr atom is linked by covalent bond to a carbon atom of the phenyl ring, and it stabilizes through of agostic hydrogen bonds.

US 5 348 299 describes catalyst systems zwitterionics that are synthesized from compounds of metallocenodialkyl and salts of the formula [R 3 NH] + [B (C 6 F 5) 4] - by protolysis. In this case the activation of C-H as successive reaction.

EP 426 637 uses a procedure in which the Lewis acid cation CPh3 + is used for the abstraction of the methyl group from the metal center. As an anion weakly coordinative acts equally B (C 6 F 5) 4 -. In this case they are used also metallocenes Cp_ {2} MR_ {2}, in which the remains R alkyl can be cyclically linked together, as per example Cp 2 Zr (2,3-dimethyl-1,3-butadiene). In this case, after protonolysis, salts of the form are produced [Cp 2 Zr-R-RH] + [B (C 6 F 5) 4] -.

EP 0687682 describes catalyst systems for special zwitterionic transition metal, which are synthesized at from metallocene-butadiene compounds, and a Lewis acid, such as tris (pentafluorphenyl) borane. These zwitterionic compounds synthesized in this way show polymerization activities comparable to compounds of metallocene, which are activated with MAO.

The zwitterionic compounds described in the EP 0687682 have the disadvantage of detaching from the surface of the support in the heterogeneized necessary for the use industrial metallocene catalysts, in the case of Dosing of the catalyst system in the reactor. This leads to a polymerization that will develop partially so homogeneous In addition, the heterogeneized of these systems catalysts leads to a polymerization activity reduced

Now there was the task of finding a compound of transition metal that will avoid the inconvenience of the state of The technique. Now it was discovered that you can fix this problem using zwitterionic transition metal compounds special. Therefore, the present invention relates to a catalyst, to a process for obtaining a polyolefin, and in addition to a zwitterionic transition metal compound of the formula I

1

where

M is titanium, zirconium or hafnium,

n is equal to 2 or 3,

L is a cyclopentadienyl ring preferably substituted, or an indenyl ring preferably substituted, may also form 2 or more indenyl ring substituents together a system of ring, and may not be bridged or bridged through Z cyclopentadienyl and indenyl rings, with

Z bridging groups of the formula M 2 R 2 R 3, where M 2 is carbon, silicon, germanium or tin, and R2 and R3, the same or different, mean alkyl with 1 to 10 carbon atoms, aryl with 6 to 14 atoms of carbon or trimethylsilyl,

X is an aromatic or non-aromatic heterocycle, with a heteroalkyl group,

And it is a hydrocarbon residue with 1 to 40 atoms of carbon, which can be halogenated with halogens,

f is equal to 0 or 1,

A is a group IIIa metal,

R1 is the same or different, and means a alkyl group, or perfluorinated aryl, and

m is equal to 2.

The metal atoms M1 and A are attached each other through the structural element X, through a link covalent or coordinative.

In the case that Y is an allyl unit, the bond of Y to the metal atom M can be a bond sig-allyl or pi-allyl, a Additional bridge is made through the structural element X, which links the metal atoms M1 and A to each other by means of a covalent or coordinative bond. This structural element X represents a heteroatom, or a heterocycle. If X is a heterocycle which contains double bonds, the X link of X to the metal atom M It can be a coordinative link.

The pi ligands are preferably group unsubstituted or substituted cyclopentadienyl, which are the same or different, and mean a cyclopentadienyl, indenyl or substituted or unsubstituted fluorenyl, may be attached between yes two remains L through a bridge Z.

A heteroatom means each atom of the Periodic System of the Elements, with the exception of carbon e hydrogen. O, S and N. are preferred.

Heterocycles can be, among others, pyrrolidines, pyrroles, indoles, imidazoles, isoindoles or benzimidazoles, substituted or unsubstituted.

Especially preferred are compounds of the formula I where

M is titanium, zirconium or hafnium,

n is equal to 2 or 3,

L is a cyclopentadienyl ring, preferably substituted, especially in position 1,3, 1,2, 1,2,4, containing 1 to 20 carbon atoms, such as alkyl with 1 to 10 carbon atoms or aryl with 6 to 20 carbon atoms, or a preferably substituted indenyl ring, especially in position 2, 4, 2,4,5, 2,4,6, 2,4,7 or 2,4,5,6 with groups that they contain 1 to 20 carbon atoms, such as alkyl with 1 to 10 atoms of carbon or aryl with 6 to 20 carbon atoms, being able to form a ring system also two or more ring substituents indenyl together. These cyclopentadienyl rings Indenyl may be un-bridged or bridged through Z. It is Especially preferred is a bridge with two remains R in position 1,

Z means bridging groups of the formula M 2 R 2 R 3, where M 2 is carbon, silicon, germanium or tin, and R2 and R3, the same or different, mean alkyl with 1 to 10 carbon atoms, aryl with 6 to 14 atoms of carbon or trimethylsilyl,

X is an aromatic or non-aromatic heterocycle, a heteroalkyl group,

And it is a hydrocarbon residue with 1 to 40 atoms of carbon, which can be halogenated with halogens, such as fluorine, chlorine, bromine or iodine, preferably perhalogenated, especially a halogenated alkyl group, especially perhalogenated, with 1 to 30 carbon atoms, such as a trifluoromethyl, pentachloroethyl group, phthafluorisopropyl or monofluorisobutyl, or a halogenated aryl group with 6 to 30 carbon atoms, such as pentafluorphenyl, 2,4,6-trifluorphenyl, heptachloronaphthyl, heptafluornaphthyl, heptafluortolyl, 3,5-bis (trifluoromethyl) phenyl, 2,4,6-tris (trifluoromethyl) phenyl, nonafluorbiphenyl or 4- (trifluoromethyl) phenyl. For and are equally preferred moieties, such as phenyl, naphthyl, anisyl, methyl, ethyl, isopropyl, butyl, tolyl, biphenyl, 2,3-dimethyl-phenyl or an allyl moiety with at least 3 carbon atoms,

A is a group IIIa metal,

R1 means a hydrocarbon moiety with 1 to 40 carbon atoms, which may be halogenated with halogen, such as fluorine, chlorine or bromine, preferably perhalogenated, especially a halogenated alkyl group, especially perhalogenated with 1 to 30 carbon atoms, such as trifluoromethyl, pentachloroethyl, heptafluorisopropyl or monofluorisobutyl or an aryl group halogenated with 6 to 30 carbon atoms, such as pentafluorphenyl, 2,4,6-trifluorphenyl, heptachloronaphthyl, heptafluornaphthyl, heptafluortolyl, 3,5-bis (trifluoromethyl) phenyl, 2,4,6-tris (trifluoromethyl) phenyl, nonafluorbiphenyl or 4- (trifluoromethyl) phenyl. For R1 are equally preferred moieties such as phenyl, naphthyl, anisyl, methyl, ethyl, isopropyl, butyl, tolyl, biphenyl or 2,3-dimethyl-phenyl and

m is equal to 2.

Compounds of formula I where

M is zirconium,

n is equal to 3,

L are the same or different, and mean a substituted cyclopentadienyl group, such as 2-methylcyclopentadienyl, 1,3-methylcyclopentadienyl, 2-n-propylcyclopentadienyl, or pentamethylcyclopentadienyl, or alkyl group, such as methyl, being joined together two remains L through a bridge Z, Z being a carbon or substituted silicon atom,

X is an unsaturated heterocycle with N as heteroatom, which is linked to M by coordinative bond,

And it is not present with f = 0,

A is a boron atom,

R1 is the same, and means a group pentafluorphenyl, and

m is equal to 2.

For the case f = 1, a compound of formula II

two

where

M is titanium, zirconium or hafnium,

n is equal to 2,

L is a cyclopentadienyl ring, preferably substituted, especially in position 1,3, 1,2, 1,2,4, containing 1 to 20 carbon atoms, such as alkyl with 1 to 10 carbon atoms or aryl with 6 to 20 carbon atoms, or a preferably substituted indenyl ring, especially in position 2, 4, 2,4,5, 2,4,6, 2,4,7 or 2,4,5,6 with groups that they contain 1 to 20 carbon atoms, such as alkyl with 1 to 10 atoms of carbon or aryl with 6 to 20 carbon atoms, being able to form a ring system also two or more ring substituents indenyl together. These cyclopentadienyl rings Indenyl may be un-bridged or bridged through Z. It is Especially preferred is a bridge with two remains R in position 1,

Z means bridging groups of the formula M 2 R 2 R 3, where M 2 is carbon, silicon, germanium or tin, and R2 and R3, the same or different, mean alkyl with 1 to 10 carbon atoms, aryl with 6 to 14 atoms of carbon or trimethylsilyl,

X may be an aromatic heterocycle or not aromatic, a heteroalkyl group. X can also be a chain of alkyl of three to five links, which is saturated or unsaturated,

And it is a formula

3

g is an integer from 0 to 37, being able to be substituted hydrogen atoms also isolated by group I rent,

A is a group IIIa metal,

R1 is the same or different, and means a alkyl group, or aryl, perfluorinated, and

m is equal to 2.

Compounds are very particularly preferred. of formula II, where

M is zirconium,

n is equal to 3,

L are the same or different, and mean a substituted cyclopentadienyl group, such as 2-methylcyclopentadienyl, 1,3-methylcyclopentadienyl, 2-n-propylcyclopentadienyl, or pentamethyl-cyclopentadienyl, or alkyl group, such as methyl, two L-moieties being linked together across a bridge Z, where Z is a substituted carbon or silicon atom,

X is an unsaturated heterocycle with N as heteroatom, which is linked to M by coordinative bond,

g is a saturated or unsaturated alkyl chain with g = 1, whose hydrogen atoms can also be substituted by alkyl group,

A is a boron atom,

R1 is the same, and means a group pentafluorphenyl, and

m equals 3.

Examples of compounds of the formula I according to the invention:

bis (cyclopentadienyl) methylcirconiomethylbis (pentafluorphenyl) pyrrolylborate,

bis (methylcyclopentadienyl) methylcirconiomethylbis (pentafluorphenyl) -pyrrolylborate,

bis (pentamethylcyclopentadienyl) methylcirconiomethylbis (pentafluorphenyl) pyrrolylborate,

bis (n-butyl-cyclopentadienyl) methylcirconiomethylbis (pentafluorphenyl) -pyrrolylborate,

bis (indenyl) methylcirconiomethylbis (pentafluorphenyl) pyrrolylborate,

bis (2-methylindenyl) methylcirconiomethylbis (pentafluorphenyl) pyrrolylborate,

bis (2-methylbenzoindenyl) methylcirconiomethylbis (pentafluorphenyl) pyrrolylborate,

(tert-Butylamido) dimethyl (tetramethyl- η5-cyclopentadienyl) silanmethyl-zirconiomethylbis (pentafluor-phenyl) pyrrolylborate,

dimethylsilandiylbis (indenyl) methylcirconiomethylbis (pentafluorphenyl) pyrrolylborat,

dimethylsilandiylbis (2-methylindenyl) methylcirconiomethylbis- (pentafluorphenyl) pyrrolylborate,

dimethylsilandiylbis (2-methylbenzoindenyl) methylcirconiomethylbis (pentafluorphenyl) pyrrolylborate,

dimethylsilandiylbis (2-methyl-4- (1-naphthyl) -indenyl) methylcirconiomethylbis (pentafluorphenyl) -pyrrolylborate,

dimethylsilandiylbis (2-methyl-4-phenyl-indenyl) methylcirconiomethylbis (pentafluorphenyl) -pyrrolylborate,

dimethylsilandiylbis (2-ethyl-indenyl) methylcirconiomethylbis (pentafluorphenyl) pyrrolylborate,

dimethylsilandiylbis (2-ethyl-4-phenyl-indenyl) methylcirconiomethylbis (pentafluorphenyl) -pyrrolylborate,

dimethylsilandiylbis (2-methyl-4 (4'-tert-butyl-phenyl) -indenyl) methylcirconiomethylbis (pentafluor-phenyl) pyrrolyl-borate,

dimethylsilandiylbis (2-methyl-4 (4'-methyl-phenyl) -indenyl) methylcirconiomethylbis (pentafluor-phenyl) pyrrolyl-borate,

dimethylsilandiylbis (2-methyl-4 (4'-iso-propyl-phenyl) -indenyl) methylcirconiomethylbis (pentafluor-phenyl) pyrrolyl-borate,

dimethylsilandiylbis (2-ethyl-4 (4'-tert-butyl-phenyl) -indenyl) methylcirconiomethylbis (pentafluor-phenyl) pyrrolyl-borate,

dimethylsilandiylbis (2-ethyl-4 (4'-hexyl-phenyl) -indenyl) methylcirconiomethylbis (pentafluor-phenyl) pyrrolylborate,

dimethylsilandiylbis (2-n-propyl-4 (4'-tert-butyl-phenyl) -indenyl) methylcirconiomethylbis (pentafluor-phenyl) pyrrolylborate,

dimethylsilandiylbis (2-n-propyl-4 (4'-methyl-phenyl) -indenyl) methylcirconiomethylbis (pentafluor-phenyl) pyrrolyl-borate,

dimethylsilandiylbis (2-n-butyl-4 (4'-tert-butyl-phenyl) -indenyl) methylcirconiomethylbis (pentafluor-phenyl) pyrrolylborate,

dimethylsilandiylbis (2-n-butyl-4 (4'-methyl-phenyl) -indenyl) methylcirconiomethylbis (pentafluor-phenyl) pyrrolyl-borate,

dimethylsilandiylbis (2-n-hexyl-4 (4'-tert-butyl-phenyl) -indenyl) methylcirconiomethylbis (pentafluor-phenyl) pyrrolylborate,

dimethylsilandiylbis (2-methyl-4, 5-benzoindenyl) methylcirconiomethylbis (pentafluorphenyl) pyrrolylborate,

dimethylsilandiylbis (2-methyl-4,6-diisopropyl-indenyl) methylcirconiomethylbis (pentafluorphenyl) pyrrolylborate,

dimethylsilandiilbis (2, 4, 6-trimethyl-indenyl) methylcirconiomethylbis (pentafluorphenyl) pyrrolylborate,

methyl (phenyl) silandiylbis (2-methylindenyl) methylcirconiomethylbis (pentafluorphenyl) pyrrolylborate,

methyl (phenyl) silandiylbis (2-methylbenzoindenyl) methylcirconiomethylbis (pentafluorphenyl) pyrrolylborate,

methyl (phenyl) silandiylbis (2-methyl-4- (1-naphthyl) -indenyl) methylcirconiomethylbis (pentafluorphenyl) -pyrrolyl-borate,

methyl (phenyl) silandiylbis (2-methyl-4-phenyl-indenyl) methylcirconiomethylbis (pentafluorphenyl) -pyrrolylborate,

methyl (phenyl) silandiylbis (2-methyl-4,5-benzoindenyl) methylcirconiomethylbis (pentafluorphenyl) -pyrrolylborate,

methyl (phenyl) silandiylbis (2-methyl-4,6-diisopropyl-indenyl) methylcirconiomethylbis (pentafluor-phenyl) pyrrolyl-borate,

methyl (phenyl) silandiilbis (2, 4, 6-trimethyl-indenyl) methylcirconiomethylbis (pentafluorphenyl) -pyrrolylborate,

diphenylmethylene- (fluorenyl) (cyclopentadienyl) methylcirconiomethylbis (pentafluorphenyl) - pyrrolylborate,

dimethylmethylene- (fluorenyl) (cyclopentadienyl) methylcirconiomethylbis (pentafluorphenyl) -pyrrolylborate,

methylphenylmethylene- (fluorenyl) (cyclopentadienyl) methylcirconiomethylbis (pentafluorphenyl) - pyrrolylborate,

ethylenebis (2-methyl-4-phenyl-indenyl) methylcirconiomethylbis (pentafluorphenyl) pyrrolylborate,

ethylenebis (2-methyl-4,5-benzoindenyl) methylcirconiomethylbis (pentafluorphenyl) pyrrolylborate,

ethylenebis (2-methyl-4,6-diisopropylindenyl) methylcirconiomethylbis (pentafluorphenyl) pyrrolylborate,

1,6- {bis [methylsilyl-bis (2-methyl-4-phenyl-indenyl) methylcirconiomethylbis (pentafluorphenyl) -pyrrolylborate} hexane,

1,6- {bis [methylsilyl-bis (2-ethyl-4-phenyl-indenyl) methylcirconiomethylbis (pentafluorphenyl) pyrrolyl-borate} hexane,

1,6- {bis [methylsilyl-bis (2-methyl-4,5-benzoindenyl) methylcirconiomethylbis (pentafluorphenyl) -pyrrolylborate} hexane,

1,6- {bis [methylsilyl (2-methyl-4-phenyl-indenyl) (2-methyl-indenylmethylcirconiomethylbis (pentafluorphenyl) pyrrolylborate} -he-
xano,

1,6- {bis [methylsilyl-bis (2-methyl-4-phenyl-indenyl) methylcirconiomethylbis (pentafluorphenyl) -pyrrolylborate} ethane,

1,6- {bis [methylsilyl-bis (2-ethyl-4-phenyl-indenyl) methylcirconiomethylbis (pentafluorphenyl) pyrrolylborate} ethane,

1,6- {bis [methylsilyl-bis (2-methyl-4-naphthylphenyl-indenyl) methylcirconiomethylbis (pentafluor-phenyl) pyrrolyl-borate} -ethane,

1,6- {bis [methylsilyl-bis (2-methyl-4,5-benzoindenyl) methylcirconiomethylbis (pentafluorphenyl) -pyrrolylborate} ethane,

1,6- {bis [methylsilyl (2-methyl-4-phenyl-indenyl) (2-methyl-indenylmethylcirconiomethylbis (pentafluorphenyl) pyrrolylborate} -
ethane,

tri (cyclopentadienyl) zirconiomethylbis (pentafluorphenyl) pyrrolylborate,

tri (methylcyclopentadienyl) zirconiomethylbis (pentafluorphenyl) pyrrolylborate,

tri (pentamethylcyclopentadienyl) zirconiomethylbis (pentafluorphenyl) pyrrolylborate,

tri (n-butyl-cyclopentadienyl) zirconiomethylbis (pentafluorphenyl) pyrrolylborate.

The corresponding ones are also preferred compounds in which pyrrole was replaced by imidazoles, benzimidazoles and indoles.

Dimethylsilandiylbis- (2-n-butyl-4 (4'-tert-butyl-phenyl) -indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluor-phenyl) -pyrrolyl-
borate,

dimethylsilandiylbis- (2-n-butyl-4 (4'-methyl-phenyl) -indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate,

dimethylsilandiylbis- (2-n-butyl-4 (4'-ethyl-phenyl) -indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate,

dimethylsilandiylbis- (2-n-butyl-4 (4'-n-propyl-phenyl) -indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate,

dimethylsilandiylbis- (2-n-butyl-4 (4'-iso-propyl-phenyl) -indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylbo-
little while,

dimethylsilandiylbis- (2-n-butyl-4 (4'-n-butyl-phenyl) -indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate,

dimethylsilandiylbis- (2-n-butyl-4 (4'-hexyl-phenyl) -indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate,

dimethylsilandiylbis- (2-n-butyl-4 (4'-sec-butyl-phenyl) -indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate,

dimethylsilandiylbis- (2-n-hexyl-4 (4'-tert-butyl-phenyl) -indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluor-phenyl) pyrrolyl-
borate,

dimethylsilandiylbis- (2-n-hexyl-4 (4'-methyl-phenyl) -indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate,

dimethylsilandiylbis- (2-n-hexyl-4 (4'-ethyl-phenyl) -indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate,

dimethylsilandiylbis- (2-n-hexyl-4 (4'-n-propyl-phenyl) -indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluor-phenyl) pyrrolylbo-
little while,

dimethylsilandiylbis- (2-n-hexyl-4 (4'-iso-propyl-phenyl) -indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluor-phenyl) -pyrrolyl-
borate,

dimethylsilandiylbis- (2-n-hexyl-4 (4'-n-butyl-phenyl) -indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate,

dimethylsilandiylbis- (2-n-hexyl-4 (4'-hexyl-phenyl) -indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate,

dimethylsilandiylbis- (2-n-hexyl-4 (4'-sec-butyl-phenyl) -indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluor-phenyl) pyrrolyl-
borate,

dimethylsilandiylbis- (2-methyl-4,5-benzoindenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

dimethylsilandiylbis- (2-methyl-4,6-diisopropyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

dimethylsilandiilbis- (2, 4, 6 trimethyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate,

dimethylsilandiylbis- (2,5,6 trimethyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

dimethylsilandiylbis- (2,4,7 trimethyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

dimethylsilandiylbis- (2-methyl-5-isobutyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

dimethylsilandiylbis- (2-methyl-5-t-butyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate,

methyl (phenyl) silandiylbis- (indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

methyl (phenyl) silandiylbis- (2-methylindenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate,

methyl (phenyl) silandiylbis- (2-methylbenzoindenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

methyl (phenyl) silandiylbis- (4-phenyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate,

methyl (phenyl) silandiylbis- (4-naphthyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

methyl (phenyl) silandiylbis- (2-methyl-4- (1-naphthyl) -indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

methyl (phenyl) silandiylbis- (2-methyl-4- (2-naphthyl) -indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

methyl (phenyl) silandiylbis- (2-methyl-4-phenyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

methyl (phenyl) silandiylbis- (2-methyl-4-t.butyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

methyl (phenyl) silandiylbis- (2-methyl-4-isopropyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

methyl (phenyl) silandiylbis- (2-methyl-4- (1-naphthyl) indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate,

methyl (phenyl) silandiylbis- (2-methyl-4-ethyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

methyl (phenyl) silandiylbis- (2-methyl-4- (acenaphthyl) -indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate,

methyl (phenyl) silandiylbis- (2,4-dimethyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate,

methyl (phenyl) silandiylbis- (2-ethyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate,

methyl (phenyl) silandiylbis- (2-ethyl-4-ethyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

methyl (phenyl) silandiylbis- (2-ethyl-4-phenyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

methyl (phenyl) silandiylbis- (2-methyl-4,5-benzoindenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

methyl (phenyl) silandiylbis- (2-methyl-4,6-diisopropyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate,

methyl (phenyl) silandiylbis- (2,4,6-trimethyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

methyl (phenyl) silandiylbis- (2,5,6-trimethyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

methyl (phenyl) silandiylbis- (2,4,7-trimethyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

methyl (phenyl) silandiylbis- (2-methyl-5-isobutyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

methyl (phenyl) silandiylbis- (2-methyl-5-t-butyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

diphenylmethylene- (fluorenyl) (cyclopentadienyl) zirconium CH2CHCHCH2 bis- (pentafluorphenyl) -pyrrolylborate,

dimethylmethylene- (fluorenyl) (cyclopentadienyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

methylphenylmethylene- (fluorenyl) (cyclopentadienyl) zirconiumCH2CHCHCH2 bis- (pentafluorphenyl) -pyrrolylborate,

dimethylsilandiyl (3-tert-butyl-cyclopentadienyl) (fuorenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

diphenylsilandiyl (3- (trimethyl) cyclopentadienyl) (fuorenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate,

ethylenebis- (indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate,

ethylenebis- (2-methyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate,

ethylenebis- (2-methyl-4-phenyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate,

ethylenebis- (2-methyl-4,5 benzoindenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate,

ethylenebis- (2-methyl-4,6 diisopropylindenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate,

1,6- {Bis [methylsilyl-bis- (2-methyl-4-phenyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate} -hexa-
no,

1,6- {bis [methylsilyl-bis- (2-ethyl-4-phenyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate} hexane,

1,6- {bis [methylsilyl-bis- (2-methyl-4-naphthylphenylindenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate} -
hexane,

1,6- {bis [methylsilyl-bis- (2-methyl-4,5-benzoindenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate} -
hexane,

1,6- {bis [methylsilyl (2-methyl-4-phenyl-indenyl) (2-methyl-indenylcirconiumCH2CHCHCH2 bis- (pentafluorphenyl) pyrrolylborate} hexane,

1,6- {bis [methylsilyl-bis- (2-methyl-4-phenyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate} -ethane

1,6- {bis [methylsilyl-bis- (2-ethyl-4-phenyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate} -ethane

1,6- {bis [methylsilyl-bis- (2-methyl-4-naphthylphenyl-indenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate} -
ethane

1,6- {bis [methylsilyl-bis- (2-methyl-4,5-benzoindenyl) zirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) -pyrrolylborate} -
ethane

1,6- {bis [methylsilyl (2-methyl-4-phenyl-indenyl) (2-methyl-indenylcirconium CH 2 CHCHCH 2 bis- (pentafluorphenyl) pyrrolylborate} ethane

tri (cyclopentadienyl) zirconiomethylbis- (pentafluorphenyl) pyrrolylborate,

tri (methylcyclopentadienyl) zirconiomethylbis- (pentafluorphenyl) pyrrolylborate,

tri (pentamethylcyclopentadienyl) zirconiomethylbis- (pentafluorphenyl) pyrrolylborate,

tri (n-butyl-cyclopentadienyl) zirconiomethylbis- (pentafluorphenyl) pyrrolylborate.

The corresponding ones are also preferred compounds in which pyrrole was replaced by imidazoles, benzimidazoles and indoles.

Dimethylsilandiyl (2-methyl-4-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) methylcirconiomethylbis- (pentafluorfe-
nil) -pyrrolylborate,

dimethylsilandiyl (2-methyl-5-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) methylcirconiomethylbis- (pentafluorfe-
nil) -pyrrolylborate,

dimethylsilandiyl (2-methyl-6-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) methylcirconiomethylbis- (pentafluorfe-
nil) -pyrrolylborate,

dimethylsilandiyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) methylcirconium-methylbis- (pen-
tafluorphenyl) -pyrrolylborate,

dimethylsilandiyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) methylcirconium-methylbis- (pen-
tafluorphenyl) -pyrrolylborate,

dimethylsilandiyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) methylcirconium-methylbis- (pen-
tafluorphenyl) -pyrrolylborate,

dimethylsilandiyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) methylcirconiomethylbis- (pentafluor-
phenyl) -pyrrolylborate,

dimethylsilandiyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) methylcirconiomethylbis- (pentafluor-
phenyl) -pyrrolylborate,

dimethylsilandiyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) methylcirconium-methyl-bis-
(pentafluorphenyl) -pyrrolylborate,

dimethylsilandiyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) methylcirconium-methyl-bis-
(pentafluorphenyl) -pyrrolylborate,

dimethylsilandiyl (2-methyl-4-thiapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) methylcirconiomethylbis- (pentafluorphenyl) -pyrrolylborate,

dimethylsilandiyl (2-methyl-5-thiapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) methylcirconiomethylbis- (pentafluorphenyl) -pyrrolylborate,

dimethylsilandiyl (2-methyl-6-thiapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) methylcirconiomethylbis- (pentafluorphenyl) -pyrrolylborate,

dimethylsilandiyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) methylcirconiomethylbis- (pentafluor-
phenyl) -pyrrolylborate,

dimethylsilandiyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) methylcirconiomethylbis- (pentafluor-
phenyl) -pyrrolylborate,

dimethylsilandiyl (2-methyl-4-oxapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) methylcirconiomethylbis- (pentafluorfe-
nil) -pyrrolylborate,

dimethylsilandiyl (2-methyl-5-oxapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) methylcirconiomethylbis- (pentafluorfe-
nil) -pyrrolylborate,

dimethylsilandiyl (2-methyl-6-oxapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) methylcirconiomethylbis- (pentafluorfe-
nil) -pyrrolylborate,

dimethylsilandiyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) methylcirconiomethylbis- (penta-
fluorphenyl) -pyrrolylborate,

dimethylsilandiyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) methylcirconiomethylbis- (penta-
fluorphenyl) -pyrrolylborate.

The corresponding ones are also preferred compounds in which pyrrole was replaced by imidazoles, benzimidazoles and indoles.

The compounds of formula I and II according to the invention can also be used supported.

The support component of the catalyst system according to the invention it can be any inert solid product, organic or inorganic, especially a porous support, such as talc, inorganic oxides, mixed oxides, and finely polymer powders divided (for example polyolefins).

Appropriate inorganic oxides are found in groups 2, 3, 4, 5, 13, 14, 15 and 16 of the periodic system of The elements. Examples of preferred oxides as support they comprise silicon dioxide, aluminum oxide, as well as oxides mixed of both elements, and corresponding mixtures of oxides. Other inorganic oxides, which can be used separately or in combination with the preferred oxidic supports mentioned last instead, they are MgO, ZrO2 or B2O3, to name just Some.

The support materials used present in general a specific surface in the range of 10 m2 / g at 1000 m 2 / g, a pore volume in the range of 0.1 ml / g to 5 ml / g, and an average particle size of 1 µm to 500 µm. Are preferred supports with a specific surface in the range from 50 µm to 500 µm, a pore volume in the interval between 0.5 ml / g and 3.5 ml / g, and an average particle size in the range from 5 µm to 350 µm. Brackets are especially preferred with a specific surface in the range of 200 m2 / g at 400 m 2 / g, a pore volume in the range between 0.8 ml / g and 3.0 ml / g, and an average particle size of 10 µm to 200 µm.

If the support material used presents by nature a low moisture content or solvent content residual, dehydration or drying can be suppressed before job. If this is not the case, as in the use of silica gel as support material, dehydration or drying is recommended. He dehydration or thermal drying of the support material can be carried out low vacuum and simultaneous inert gas overlap (for example nitrogen). The drying temperature is in the interval between 100ºC and 1000ºC, preferably between 200ºC and 800ºC. In this case no The pressure parameter is decisive. The drying process time is It can be between 1 and 24 hours. Drying times are possible more short or longer, assuming that the adjustment of equilibrium with hydroxyl groups on the support surface under the selected conditions, which normally requires between 4 and 8 hours.

It is also possible to dehydrate or dry the chemical support material, reacting water adsorbed and the hydroxyl group on the surface with reagents of appropriate inert. By reacting with the reagent of inertized the entire hydroxyl groups can be transformed, or also partially, in a way that does not lead to an interaction negative with catalytically active centers. The agents of suitable inertized are, by way of example, halides of silicon and silanes, such as silicon tetrachloride, chlorotrimethylsilane, dimethylaminotriclorosilane, or compounds organometallic aluminum, boron and magnesium, such as trimethylaluminum,  triethylaluminum, triisobutylaluminum, triethylborane, dibutyl magnesium Chemical dehydration or inerting of support material can be made, by way of example, by becoming react, under exclusion of air and moisture, a suspension of support material in an appropriate solvent with the reagent pure inert, or dissolved in an appropriate solvent. Appropriate solvents are aliphatic hydrocarbons or aromatic, such as pentane, hexane, heptane, toluene or xylene. He inertized is carried out at temperatures between 25ºC and 120ºC, preferably between 50 ° C and 70 ° C. More temperatures are possible high and smaller. The reaction time is between 30 minutes and 20 hours, preferably 1 to 5 hours. After development Complete of the chemical dehydration the support material is isolated by filtration under inert conditions, one or more washes are washed times with appropriate inert solvents described above, and It is then dried in a stream of inert gas or under vacuum.

Organic support materials, such as finely divided polyolefin (for example polyethylene, polypropylene or polystyrene), can also be used, and can they will also release adhering moisture, solvent residue or other impurities through corresponding operations of purification and drying before use.

The present invention also relates to a procedure for obtaining a polyolefin by polymerization of one or more olefins in the presence of the system catalyst according to the invention, which contains at least one metallocene of the formula I. The term "polymerization" means a homopolymerization, as well as a copolymerization.

Preferably, olefins of the formula R m -CH = CH-R n, where R_ {m} and R_ {n} are the same or different and mean a hydrogen atom or a hydrocarbon residue with 1 to 20 atoms of carbon, especially 1 to 10 carbon atoms, and R m and R n they can form one or several rings together with the atoms that unite

Examples of appropriate olefins are 1-olefins with 2 to 40 carbon atoms, preferably 2 to 10 carbon atoms, such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, styrene, dienes, as 1,3-butadiene, 1,4-hexadiene, vinyl norborneno, norbornadieno, ethylnorbornadieno, and olefins cyclic, such as norbornene, tetracyclododecene or methylnorbornene. In the process according to the invention is homopolymerized preferably propene or ethene, or propene is copolymerized with ethene and / or with one or more 1-olefins with 4 to 20 carbon atoms, such as hexene, and / or one or several dienes with 4 to 20 carbon atoms, such as 1,4-butadiene, norbornadieno, ethylidennorborneno or ethylnorbornadieno. The suitable copolymers are ethene / propene copolymers or terpolymers of ethene / propene / 1,4-hexadiene.

The polymerization is carried out at a temperature from -60ºC to 300ºC, preferably 50º to 200ºC, very especially 50 ° C to 80 ° C. The pressure rises to 0.5 bar until 2000 bar, preferably 5 bar to 64 bar.

Polymerization can be carried out in dissolution, in bulk, in suspension or in the gas phase, continuous or discontinuously, in one or several stages.

The catalyst system synthesized according to the invention can be used as the sole catalyst component for the polymerization of olefins with 2 to 20 carbon atoms, or preferably in combination with at least one alkyl compound of the elements of the main group I to III of the Periodic System, as an aluminum, magnesium or lithium alkyl, or an aluminoxane. He alkyl compound is added to the monomer or suspending agent, and serves for the purification of the monomer of substances, which They can reduce catalyst activity. The amount of compound alkyl added depends on the quality of the monomers employees.

If necessary, hydrogen is added as molecular weight regulator and / or for increasing the activity.

In the polymerization can be introduced with dosing in addition an antistatic together with, or separately from catalyst system used in the polymerization system.

It is also possible to use mixtures of two or more transition metal compounds of the formula I and / or the formula II. In this way, polyolefins with distribution of wide or multimodal molecular weight.

In polymerization may be present in addition, optionally, other compounds with activity Cocatalytic The cocatalyst component, which may be contained  in the catalyst system according to the invention, it contains at least one compound of the type of an aluminoxane or a Lewis acid, or a ionic compound, which transforms it into a cationic compound by reaction with a metallocene.

As aluminoxane, preferably a compound of the general formula (III)

(III). (R AlO) n

Other appropriate aluminoxanes may be, by example, cyclic, as in formula (IV)

       \ vskip1.000000 \ baselineskip
    

4

or linear, as in the formula (V)

5

or Cluster type, as in the formula (SAW)

6

Such compounds are described, by way of example, in JACS 117 (1995), 6,465-74, Organometallics 13 (1994), 2,957- 2,969.

The R residues in formulas (III), (IV), (V) and (VI) can be the same or different, and mean a group hydrocarbon with 1 to 20 carbon atoms, as an alkyl group with 1 to 6 carbon atoms, an aryl group with 6 to 18 atoms of carbon, benzyl or hydrogen, and p means an integer from 2 to 50, preferably 10 to 35.

The R residues are preferably the same, and they mean methyl, isobutyl, n-butyl, phenyl or benzyl, especially preferably methyl.

If the R remains are different, these are preferably methyl and hydrogen, methyl and isobutyl or methyl and n-butyl, hydrogen content, or isobutyl or n-butyl preferably in a 0.01 a 40% (number of R remains).

The aluminoxane can be obtained from different ways. According to a known method, a compound is reacted of aluminum hydrocarbon and / or a hydrocarbon compound of aluminum hydride with water (gas, solid, liquid or bonded - by way of example as crystallization water) in a solvent inert (for example toluene).

To obtain an aluminoxane with different alkyl groups R are reacted with water, corresponding to the desired composition and reactivity, two different aluminum trialkyls (AlR 3 + AlR '3) (see S. Pasynkiewicz, Polyhedron 9 (1990) 429 and PE-A 302 424).

Regardless of the type of procurement, everyone aluminoxane solutions a variable content is common in starting compound of non-transformed aluminum, presented in free form or as adduct.

It is preferably used as Lewis acids at minus an organic compound of boron or aluminum, which contains groups hydrocarbon with 1 to 20 carbon atoms, such as alkyl or alkyl branched or unbranched halogenated, such as methyl, propyl, isopropyl, isobutyl, trifluoromethyl, unsaturated groups, as aryl or halogenated aryl, such as phenyl, tolyl, benzyl groups, p-fluorphenyl, 3,5-difluorphenyl, pentachlorophenyl, pentafluorphenyl, 3,4,5-trifluorphenyl and 3,5-di (trifluoromethyl) phenyl.

Examples of Lewis trimethylaluminum acids, triethylaluminum, triisobutylaluminum, tributylaluminum, trifluorborane, triphenylborane, tris (4-fluorphenyl) borane, tris (3,5-difluorphenyl) borane, tris (4-fluorphenyl) borane, tris (pentafluorphenyl) borane, tris (tolil) borane, tris (3,5-dimethylphenyl) borane, tris (3,5-difluorphenyl) borane and / or tris (3,4,5-trifluorphenyl) borane. Is especially preferred tris (4-fluorphenyl) borane.

They are preferably used as cocatalysts Ionic compounds that contain a non-coordinating anion, such as tetrakis (pentafluorphenyl) borates, tetraphenylborates, SbF_ {6} -, CF 3 {SO3 {3} - or ClO4 {-}. Is used as Lewis acid cationic counterion, such as methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline,  triethylphosphine, triphenylphosphine, diphenylphosphine, tetrahydrothiophene and triphenylcarbenium.

Examples of such ionic compounds are

tetra (phenyl) borate triethylammonium,

tetra (phenyl) borate tributylammonium,

tetra (phenyl) borate trimethylammonium,

tetra (tolyl) borate tributylammonium,

tetra (pentafluorphenyl) borate tributylammonium,

tetra (pentafluorphenyl) aluminate tributylammonium,

tetra (dimethylphenyl) borate tripropylammonium,

tetra (trifluoromethylphenyl) borate tributylammonium,

tetra (4-fluorphenyl) borate of tributylammonium,

tetra (phenyl) borate N, N-dimethylanilinium,

tetra (phenyl) borate N, N-diethylanilinium,

tetrakis (pentafluorphenyl) borate N, N-dimethylanilinium,

tetrakis (pentafluorphenyl) aluminate of N, N-dimethylanilinium,

tetrakis (pentafluorphenyl) borate di (propyl) ammonium,

tetrakis (pentafluorphenyl) borate di (cyclohexyl) ammonium,

tetrakis (phenyl) borate triphenylphosphonium,

tetrakis (phenyl) borate triethylphosphonium,

tetrakis (phenyl) borate diphenylphosphonium,

tetrakis (phenyl) borate tri (methylphenyl) phosphonium,

tetrakis (phenyl) borate tri (dimethylphenyl) phosphonium,

tetrakis (pentafluorphenyl) borate triphenylcarbenium,

tetrakis (pentafluorphenyl) aluminate of triphenylcarbenium,

tetrakis (phenyl) aluminate triphenylcarbenium,

tetrakis (pentafluorphenyl) borate ferrocenium and / or

tetrakis (pentafluorphenyl) aluminate of ferrocenium.

Are preferred triphenylcarbenium tetrakis (pentafluorphenyl) borate and / or tetrakis (pentafluor-phenyl) borate of N, N-dimethylanilinium.

It is also possible to use mixtures of at least one Lewis acid and at least one ionic compound.

As cocatalyst components they are also significant compounds of borane or carborane, such as 7,8-dicarbaundecarborano (13), undecahydride-7,8-dimethyl-dicarbaundecaborane, dodecahydride-1-phenyl-1,3-dicarbonaborane, decahydride-8-ethyl-7,9-dicarbaundecaborate of tri (butyl) -ammonium, 4-carbanonaborane (14), nonaborate bis (tri (butyl) ammonium) undecaborate bis (tri (butyl) ammonium), dodecaborate bis (tri (butyl) ammonium), decachlorochlorocaborate of bis (tri (butyl) -ammonium), Tri (butyl) ammonium 1-carbadecaborate, 1-Carbohydrate tri (butyl) ammonium, 1-trimethylsilyl-1-carbadecaborate of tri (butyl) ammonium, bis (nonahydride-1,3-dicarbononaborate) cobaltate (III) of tri (butyl) ammonium, bis (undecahydride-7,8-dicarbaundecaborate) ferrate (III) of tri (butyl) ammonium.

A previous polymerization can be carried out with aid of the compounds of the formula I and II. For the Prior polymerization is preferably used the (or one of the) olefin (s) used in the polymerization.

The following examples are for the Explanation of the invention

General data: obtaining and handling were carried out of compounds under exclusion of air and moisture under gas of argon protection (Schlenk technique). Before employment is dehydrated all the solvents required by boiling of several hours on appropriate drying agents, and subsequent distillation under argon.

The synthesis of butadiene complexes is carried out according to G. Erker, K. Engel, Ch. Sarter in R.B. King, J.J. Eisch, Organometallics Synthesis, Vol 3, Academic Press, New York 1986, 529

The synthesis of pyrrolidinylboro dichloride is Performs according to K. Niederzu, J. Am. Chem. Soc., 1959, 81, 5,553. The fluoride complex synthesis of (pentafluorphenyl) boron ether is performed according to M. Bochmann, Organometallics, 1997, 16, 4,995. The synthesis of tris (η 5 -cyclopentadienyl) methylcirconium it is done according to Brackemeyer, G. Erker, R. Fröhlich, Organometallics 1997, 16, 531.

Compounds were characterized with 1 H-NMR spectroscopy, 13 C-NMR and IR.

Example 1 Synthesis of bis (pentafluorphenyl) pyrrolylborane

It is added to 140 ml (72.8 mmol) of a solution of fluoride complex bis (pentafluorphenyl) boron-ether / ether 0.52 M at -78 ° C, carefully, a suspension of 5,316 g (72.8 mmol) of pyrrolidyllithium in 50 ml of ether in portions. It heats up reaction mixture slowly at room temperature, stir 14 more hours Then the solvent is changed from ether to pentane. He the precipitate is filtered off, and the solid product is washed twice with 20 ml of pentane. It is concentrated by evaporation yellowish, clear pentane phase, until they can be identified the first germs of crystallization, and the same is preserved at 8ºC. By fractional crystallization at 8 ° C the product as colorless crystals. Yield: 15.6 g (38.0 mmoles), 52%).

Elementary analysis (%) for C 16 H 4 NBF 10 (Mr = 411.0): calculated: C 46.76, H 0.98, N 3.41; Found: C 46.58, 1.25, N 3.30.

1H-NMR (200.13 MHz, C 6 D 6, 300 K): δ = 6.59 (m, 2H, H (2.5)), 6.23 (m, 2H, H (3.4)).

13C-NMR (75.47 MHz, C 6 D 6, 300 K): δ = 147.1 (dm, 1 J (F, C) = 256.7 Hz, ArF_ ortho), 143.4 (dm, 1J (F, C) = 239.6 Hz, ArF_para}, 138.1 (dm, 1J (F, C) = 254.3 Hz, ArF_ meta),  127.7 (C (2.5)), 118.3 (C (3.4)), 110.0 (width, C_ {ipso}).

11B-NMR (64.21 MHz, C 6 D 6, 300K): δ = 40.8 (40 1/2) = 480 Hz)

14N-NMR (14.47 MHz, C_ {6} D_ {6}, 300K): δ = -176 (\ nu 1/2 = 510 Hz)

19F-NMR (282.41 MHz, C_ {6} D_ {6}, 300K): δ = -130.5 (m, 2F, F_ {meta}), -148.4 (t, 1F, F_), -160.0 (m, 2F, F_ ortho).

Example 2 Synthesis of bis (η 5 -cyclopentadienyl) methylcirconiomethylbis (pentafluorphenyl) pyrrolylborate

0.133 g (0.529 mmol) of bis (η 5 -cyclopentadienyl) dimethylcirconium and 0.217 g (0.529 mmol) of bis (pentafluorphenyl) pyrrolylborane, at temperature ambient, in 10 ml of toluene, and stir 5 minutes. Then The solvent is removed in vacuo. The precipitate is absorbed Remain with 20 ml of pentane, and stir 10 minutes. After filtration of the yellow suspension, and double washing of the residue with 5 ml of pentane respectively, the product is obtained as yellow powder Yield: 0.217 g (0.284 mmol); 62%)

1H-NMR (200.13 MHz, C 6 D 6, 300 K): δ = 7.22 (m, 2H, H (2.5)), 5.22 (m, 2H, H (3.4)), 5.15 (s, 10H, Cp), 1.11 (width m, 3H, BMe), - 0.03 (s, 3H, ZrMe).

1H-NMR (599.9 MHz, C 7 D 8, 298 K): δ = 7.15 (m, 2H, H (2.5)), 5.14  (m, 2H, H (3.4)), 5.14 (s, 10H, Cp), 0.99 (width m, 3H, BMe), - 0.10 (s, 3H, ZrMe).

1H-NMR (599.9 MHz, C 7 D 8, 253 K): δ = 7.20 (m, 2H, H (2.5)), 5.05  (m, 2H, H (3.4)), 5.04 (s, 10H, Cp), 1.10 (width m, 3H, BMe), - 0.11 (s, 3H, ZrMe).

13C-NMR (75.47 MHz, C_ {6} D_ {6}, 300 K): δ = n.o. (ArF_ {ortho}, ArF_ {meta}, ArF_ {para}), n.o. (C_ {ipso}), 139.0 (C (2.5)), 112.4 (Cp), 99.6 (C (3.4)), 37.5 (ZrMe), 10.9 (width, BMe).

13C-NMR (125.9 MHz, C 7 D 8, 298 K): δ = 148.6 (dm, 1 J (F, C) = 248 Hz, ArF_ ortho), 139.3 (dm, 1J (F, C) = 250 Hz, ArF_para}, 139.2 (C (2.5)), 137.7 (dm, 1J (F, C) = 246 Hz, ArF_ {meta}), no. (C_ {ipso}), 112.5 (Cp), 99.4 (C (3.4)), 37.3 (ZrMe), 10.5 (width, BMe).

13C-NMR (125.9 MHz, C 7 D 8, 253 K): δ = 148.3 (dm, 1 J (F, C) = 242 Hz, ArF_ ortho), 139.1 (dm, 1J (F, C) = 239 Hz, ArF_para}, 139.8 (C (2.5)), 137.5 (dm, 1J (F, C) = 248 Hz, ArF_ {meta}), no. (C_ {ipso}), 112.1 (Cp), 98.4 (C (3.4)), 36.4 (ZrMe), 10.5 (width, BMe).

11B-NMR (64.21 MHz, C_ {6} D_ {6}, 300K): δ = -6.7 (\ nu ^ {1/2} = 192 Hz)

19F-NMR (282.41 MHz, C_ {6} D_ {6}, 300K),: δ = -132.5 (m, 2F, F_ {meta}), -159.6 (t, 1F, F_), -163.9 (m, 2F, F_ ortho).

Example 3 Synthesis of tris (η 5 -cyclopentadienyl) zirconiomethylbis (pentafluorphenyl) pyrrolylborate

0.132 g (0.438 mmol) of tris (η 5 -cyclopentadienyl) methylcirconium and 0.188 g (0.438 mmol) of bis (pentafluorphenyl) pyrrolylborane, at temperature ambient, in 10 ml of toluene, and stir 1.5 hours. Then The solvent is removed in vacuo. The precipitate is absorbed remaining with 30 ml of pentane, and stir 3 hours. After filtration of the yellow suspension, and double washing of the residue with 10 ml of pentane respectively, the product is obtained as yellow powder.  Yield: 0.223 g (0.313 mmol); 71%).

Crystallization from benzene provides monocrystals for structural analysis by X-rays.

1H-NMR (200.13 MHz, C 6 D 6, 300 K): δ = 7.65 (m, 2H, H (2.5)), 5.58 (m, 2H, H (3.4)), 4.94 (s, 15H, Cp), 1.28 (width m, 3H, BMe).

1H-NMR (599.2 MHz, C 6 D 6, 298 K): δ = 7.65 (width, 2H, H (2.5)), 5.58 (width, 2H, H (3.4)), 4.94 (s, 15H, Cp), 1.27 (width m, 3H, BMe).

13C-NMR (125.9 MHz, C 6 D 6, 298 K): δ = 148.7 (dm, 1 J (F, C) = 236 Hz, ArF_ ortho), 142.5 (width C (2.5)), 139.3 (dm, 1J (F, C = 239 Hz, ArF_para), 137.6 (dm, 1J (F, C) = 249 Hz, ArF_ {meta}), n, b, (C_ {ipso}), 113.5 (Cp), 113.4 (slightly widened, C (3,4)), 10,9 (wide, BMe).

11B-NMR (64.21 MHz, C_ {6} D_ {6}, 300K): δ = -6.8 (\ nu 1/2 = 188 Hz)

19F-NMR (282.41 MHz, C 6 D 6, 300K): δ = -132.4 (m, 2F, F_ {meta}), -159.9 (t, 1F, F_), -164.1 (m, 2F, F_ ortho).

Example 4 Synthesis of bis (η 5 -cyclopentadienyl) zirconium CH 2 CHCHCH 2 bis (pentafluorphenyl) pyrrolylborate

0.120 g (0.436 mmol) of (s-cis / s-trans- η 4 -butadien) bis (η 5 -cyclopentadienyl) zirconium and 0.179 g (0.436 mmol) of bis (pentafluorphenyl) pyrrolylborane, at temperature ambient, in 10 ml of toluene, and stir 1 hour. Then you Remove solvent in vacuo. The remaining precipitate is absorbed with 30 ml of pentane, and stir 3 hours. After filtration of the yellow suspension, and double washing of the residue with 10 ml of pentane respectively, the product is obtained as yellow powder. Yield: 0.195 g (0.284 mmol); 65%)

1H-NMR (599.2 MHz, CD_2C_ {l2}, 298K): δ = 7.63 (width, 1H, H (α)), 7.22 (width, 1H, H (β)), 6.46 (width, 1H, H (β ')), 5.89 (s, 5H, Cp'), 5.57 (width, 1H, H (α ')), 5.54 (ddd, 3J (H, H) = 16.0 Hz 3J (H, H) = 12.7 Hz 3J (H, H) = 8.0 Hz, 1H, H (2)), 5.24 (s, 5H, Cp), 4.34 (dd, 3J (H, H) = 16.0 Hz 3J (H, H) = 10.5 Hz, 1H, H (3)), 2.71 (d, 2J (H, H) = 16.0 Hz, 1H, H (4 ')), 2.60 (dd, 2J (H, H) = 4.9 Hz 3J (H, H) = 8.0 Hz, 1H, H (1 ')), 2.29 (dd, 2J (H, H) = 16.0 Hz, 3J (H, H) = 10.5 Hz, 1H, H (4)), 1.90 (dd, 2J (H, H) = 4.9 Hz 3J (H, H) = 12.7 Hz, 1H, H (1)).

13C-NMR (150.7 MHz, CD_ {2} C_ {l2}, 298K): δ = 147.4 (width, C (? ')), 133.1 (width, C (?)), 120.8 (C (2)), 114.0 (C (3)), 110.5 (Cp), 108.0 (Cp '), 95.0 (width, C (β)), 47.8 (C (1)), 28.3 (width, C (4)).

13C-NMR (150.7 MHz, CD_ {2} C_ {l2}, 213K): δ = 147.0 (dm, 1J (F, C) = 232 Hz, ArF_ ortho), 144.1 (C (?)), 137.8 (dm, 1J (F, C) = 240 Hz, ArF_ for}, 136.5 (dm, 1J (F, C) = 248 Hz, ArF_ meta), 133.2 (C (?)), 121.0 (C (2)), 112.9 (width, C_ {ipso}), 110.0 (C (3)), 109.8 (Cp), 109.4 (C (β ')), 107.1 (Cp'), 92.1 (C (β)), 47.0 (C (1)), 26.6 (width, C (4)).

11B-NMR (64.21 MHz, C_ {6} D_ {6}, 300K): δ = -7.3 (\ nu 1/2 = 185 Hz)

19F-NMR (282.41 MHz, C_ {D} {8}, 300K): δ = -131.2 (m, 2F, F_ {meta}), -133.4 (m, 2F, F_ {meta}), -158.7 (t, 1F, F_ {para}), -160.0 (t, 1F, F_), -163.4 (m, 2F, F_ ortho), -164.0 (m, 2F, F_ {ortho}).

Example 5 Homogenous polymerization of ethene with bis (η 5 -cyclopentadienyl) methylcirconium-methylbis (pentafluorphenyl) pyrrolylborate

16 mg (0.06 mmol) of bis (η 5 -cyclopentadienyl) dimethylcirconium and 26 mg (0.06 mmol) of bus (pentafluorphenyl) pyrrolylborane at temperature Ambient in 10 ml of toluene, mix with 3.5 ml of TIBA, and mix stir 10 minutes subsequently. Then it loads this solution in a 300 ml polymerization autoclave (Parr 4560) for polymerization. It polymerizes at 25 ° C, and at a pressure of ethene of 10 bar 60 minutes. The polymer is dried in a closet vacuum dryer 12 g of polyethylene result. The activity of catalyst amounts to 0.75 kg of PE / g of metallocene x h.

Example 6 Homogenous polymerization of ethene with bis (η 5 -cyclopentadienyl) zirconium CH 2 CHCHCH 2 bis (pentafluorphenyl) pyrrolylborate

14 mg (51 µm) of (s-cis / s-trans- η 4 -butadien) bis (η 5 -cyclopentadienyl) zirconium with 21 mg (51 µm) of bis (pentafluorphenyl) pyrrolylborane in 15 ml of toluene, and mix with 5 ml of TIBA. Stir 15 minutes so subsequent. This solution is then loaded into a reactor stirring 1.5 dm3 for polymerization. It polymerizes to  room temperature, and at an ethene pressure of 35 bar 60 minutes The polymer is dried in a vacuum dryer cabinet. Result 16 g of polyethylene. The catalyst activity amounts to 1.14 kg of PE / g of metallocene x h.

Example 7 Homogeneous polymerization of propene with bis (η 5 -cyclopentadienyl) zirconium CH 2 CHCHCH 2 bis (pentafluorphenyl) pyrrolylborate

42 mg (153 µm) of (s-cis / s-trans- η 4 -butadien) bis (η 5 -cyclopentadienyl) zirconium with 63 mg (153 µm) of bis (pentafluorphenyl) pyrrolylborane in 15 ml of toluene, and stir 15 minutes. In parallel, a reactor was swept dry 2 liters first with nitrogen, and then with propylene, and it was loaded with 1.5 liters of liquid propylene. He They added 5 ml of TIBA (20% in varsol), and stirred 15 minutes. Then the catalyst solution obtained is added to the reactor. The reaction mixture is heated to the temperature of polymerization of 60 ° C, and polymerizes 1 hour. The polymerization by degassing of the remaining propylene. He Dry the polymer in a vacuum dryer cabinet. 172 g of Polypropylene. The catalyst activity amounts to 4.1 kg of PP / g of metallocene x h.

Example 8 Heterogeneous polymerization of propene with bis (η 5 -cyclopentadienyl) zirconium CH 2 CHCHCH 2 bis (pentafluorphenyl) pyrrolylborate

3 g of SiO2 were suspended (MS 3030, signature PQ, drying at 600 ° C in argon stream) in 15 ml of toluene, and they were mixed drop by drop, under stirring slowly, with a 147 mg solution (0.535 mmol) of (s-cis / strans- η 4 -butadien) bis (η 5 -cyclopentadienyl) zirconium and 221 mg (0.535 mmol) of bis (pentafluorphenyl) pyrrolylborane in 5 ml of toluene. It was stirred one hour at room temperature, and then the Vacuum solvent of oil pump until proof of weight. 1 g was resuspended for inclusion in the polymerization system of catalyst supported in 30 cm 3 of Exxsol.

Polymerization

In parallel, a dry reactor of 16 was swept dm3 first with nitrogen, and then with propylene, and was charged with 10 dm 3 of liquid propylene. Then 0.5 cm 3 of a solution of 20% triisobutylaluminum in Varsol, diluted with 30 cm3 of Exxsol, and the charge was stirred at 30 ° C for 15 minutes. Then you He added the catalyst suspension to the reactor. It warmed up reaction mixture at polymerization temperature of 60 ° C (4 ° C / min) and the polymerization system was maintained for 1 h by cooling at 60 ° C. Polymerization was stopped by degassing of the remaining propylene. The polymer was dried in vacuum dryer cabinet. 182 g of powder were obtained Polypropylene. The reactor showed no deposits in the inner wall or on the stirrer. The catalyst activity amounted to 3.7 kg of PP / g of metallocene x h.

Claims (8)

1. Zwitterionic transition metal compound of the formula I 7 where M is titanium, zirconium or hafnium, n is equal to 2 or 3, L is a cyclopentadienyl ring preferably substituted, or an indenyl ring preferably substituted, may also form 2 or more indenyl ring substituents together a system of ring, and may not be bridged or bridged through Z cyclopentadienyl and indenyl rings, with Z bridging groups of the formula M 2 R 2 R 3, where M 2 is carbon, silicon, germanium or tin, and R2 and R3, the same or different, mean alkyl with 1 to 10 carbon atoms, aryl with 6 to 14 atoms of carbon or trimethylsilyl, X is an aromatic or non-aromatic heterocycle, with a heteroalkyl group, And it is a hydrocarbon residue with 1 to 40 atoms of carbon, which can be halogenated with halogens, f is equal to 0 or 1, A is a group IIIa metal, R1 is the same or different, and means a alkyl group, or perfluorinated aryl, and m is equal to 2. 2. Compound of formula I according to claim 1, wherein M is zirconium, n is equal to 3, L are the same or different, and mean a substituted cyclopentadienyl group, such as 2-methylcyclopentadienyl, 1,3-methylcyclopentadienyl, 2-n-propylcyclopentadienyl, or pentamethylcyclopentadienyl, or alkyl group, such as methyl, being joined together two remains L through a bridge Z, Z being a carbon or substituted silicon atom, X is an unsaturated heterocycle with N as heteroatom, which is linked to M by coordinative bond, And it is not present with f = 0, A is a boron atom, R1 is the same, and means a group pentafluorphenyl, and m is equal to 2. 3. Compound of formula I according to claims 1 to 2, wherein And it is a formula 8 g is an integer from 0 to 37, being able to be substituted hydrogen atoms also isolated by group I rent. 4. Catalyst containing at least one compound according to one of claims 1 to 3, as well as a Cocatalyst 5. Procedure for obtaining a polyolefin in the presence of a compound according to one of the claims 1 to 3. 6. Procedure for obtaining a polyolefin in the presence of a catalyst according to claim Four. 7. Use of a compound according to one of the claims 1 to 3 for the polymerization of olefins. 8. Use of a catalyst according to claim 4 for the polymerization of olefins.